JPH08175B2 - Method for producing sulfonated polysulfone film forming material - Google Patents
Method for producing sulfonated polysulfone film forming materialInfo
- Publication number
- JPH08175B2 JPH08175B2 JP61283935A JP28393586A JPH08175B2 JP H08175 B2 JPH08175 B2 JP H08175B2 JP 61283935 A JP61283935 A JP 61283935A JP 28393586 A JP28393586 A JP 28393586A JP H08175 B2 JPH08175 B2 JP H08175B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- sulfonated polysulfone
- forming material
- water
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、スルホン化ポリサルホン膜形成材料の製造
法に関する。更に詳しくは、限外ロ過膜形成などに用い
られるスルホン化ポリサルホン膜形成材料の製造法に関
する。TECHNICAL FIELD The present invention relates to a method for producing a sulfonated polysulfone film forming material. More specifically, it relates to a method for producing a sulfonated polysulfone film forming material used for forming an ultrafiltration membrane.
限外ロ過は、液中に分散した微量油分、細菌、その他
の微粒子を取り除くための唯一の省エネルギー分離プロ
セスであり、種々の分野で使用されている。Ultrafiltration is the only energy-saving separation process for removing trace amounts of oil, bacteria, and other fine particles dispersed in a liquid, and is used in various fields.
この限外ロ過において、膜面へ堆積、吸着される物質
はしばしば膜の目詰りをひき起し、その結果として膜の
抵抗を高め、ロ過効率を低下させる。そのため、膜の運
転方法はクロスフロー方式をとり、なるべく膜面への堆
積を抑えるようにしている。In this ultrafiltration, substances deposited and adsorbed on the film surface often cause the film to be clogged, resulting in an increase in the film resistance and a decrease in the filtration efficiency. Therefore, the operation method of the film is a cross flow method, and the deposition on the film surface is suppressed as much as possible.
しかしながら、膜表面はやはり汚染を受け、透過抵抗
が徐々に上昇してくる現象がみられる。これは、ロ過対
象液中の分散物質が膜表面へ吸着し、膜の孔を塞ぐため
に起るものと考えられる。このような物質は、一旦膜表
面へ吸着されると、逆洗および洗浄などをしても膜から
離れず、いわゆるプラギング現象を起し、最後には膜の
透過率が殆んどゼロとなってしまう。However, the membrane surface is still contaminated, and the permeation resistance gradually increases. It is considered that this occurs because the dispersed substance in the liquid to be filtered is adsorbed on the surface of the membrane and blocks the pores of the membrane. Once such a substance is adsorbed on the membrane surface, it does not separate from the membrane even if it is backwashed and washed, so-called plugging phenomenon occurs, and finally the membrane transmittance becomes almost zero. Will end up.
ここで、このような物質の性状について考察するに、
水中に安定分散し、膜でのみしか除去できない物質は、
粒子相互のもつ電気的な反発作用で安定化しているもの
と考えられ、自然界ではそれぞれの粒子が負電荷をもっ
ているものが多い。Here, to consider the properties of such substances,
Substances that are stably dispersed in water and can be removed only by a membrane are
It is considered that the particles are stabilized by the electrical repulsion between them, and in nature, each particle often has a negative charge.
そこで、膜表面にこのような粒子を吸着し難くするた
めには、膜表面の負電荷を豊富にするためにあるいは親
水性にするために膜表面の水和層の厚さを増すなどの方
法が考えられ、このために膜材料として有望なポリサル
ホンにスルホン基を導入することが試みられている。し
かしながら、膜材料に極性基を導入する手法には、次の
ような欠点がある。Therefore, in order to make it difficult for such particles to be adsorbed on the membrane surface, a method such as increasing the thickness of the hydrated layer on the membrane surface in order to enrich the negative charges on the membrane surface or to make it hydrophilic Therefore, introduction of a sulfone group into polysulfone, which is a promising membrane material, has been attempted for this purpose. However, the method of introducing a polar group into the film material has the following drawbacks.
（１）膜の親水性が高まるにつれ、水中での膜強度が低
下する。(1) As the hydrophilicity of the film increases, the film strength in water decreases.
（２）製膜時に水をゲル化浴として用いることが多いた
め、ゲル化の際水を抱き込んで重合体が凝集してしま
い、そのため極性基の導入率を高くすると膜を形成せ
ず、製膜が不可能となる。(2) Since water is often used as a gelling bath at the time of film formation, the polymer is aggregated by embracing water during gelation. Therefore, if the introduction rate of polar groups is increased, a film is not formed, Film formation becomes impossible.
このような欠点を解消し、しかも透水性にすぐれたポ
リサルホン樹脂系限外ロ過膜を求めて種々検討の結果、
ポリサルホンにスルホン化ポリサルホンを混合して用い
ることにより、かかる課題が効果的に解決されること
を、本出願人は先に見出している（特願昭60−93318
号）。As a result of various investigations in order to solve such drawbacks and to obtain a polysulfone resin-based ultrafiltration membrane having excellent water permeability,
The present applicant has previously found that such problems can be effectively solved by using polysulfone mixed with sulfonated polysulfone (Japanese Patent Application No. 60-93318).
issue).
上記提案においては、一応所期の目的は達成されるも
のの、重合体くり返し単位当りのスルホン化度が0.75〜
1.5のスルホン化ポリサルホンがポリサルホン100重量部
当り約５〜30重量部の割合で混合された混合物として用
いられているためスルホン化度が低下し、そのため耐汚
染効果が必ずしも十分に発揮されないという難点もみら
れた。In the above proposal, although the intended purpose is achieved for the time being, the degree of sulfonation per polymer repeating unit is 0.75 to
Since the sulfonated polysulfone of 1.5 is used as a mixture in which it is mixed at a ratio of about 5 to 30 parts by weight per 100 parts by weight of polysulfone, the degree of sulfonation is reduced, and therefore the stain resistance effect is not always sufficiently exhibited. Was given.
そこで、本発明者らは上記（１）および（２）にみら
れるような膜形成上の欠点を克服し、スルホン化ポリサ
ルホン単体から水中に長時間放置しても安定な膜を形成
し得る材料が得られるような方法を求めて種々検討を重
ねた結果、スルホン化ポリサルホンを一旦非プロトン性
極性溶媒−水混合溶媒溶液に調製した後、それを特定の
界面活性剤水溶液とを混合し、スルホン化ポリサルホン
を沈殿させることにより、かかる課題が効果的に解決さ
れることを見出した。Therefore, the present inventors have overcome the drawbacks in film formation as seen in the above (1) and (2), and can form a stable film from a sulfonated polysulfone simple substance even if it is left in water for a long time. As a result of various investigations for obtaining a method for obtaining a sulfonated polysulfone, the sulfonated polysulfone was once prepared into an aprotic polar solvent-water mixed solvent solution, which was then mixed with a specific surfactant aqueous solution to give a sulfone. It has been found that such a problem can be effectively solved by precipitating the modified polysulfone.
従って、本発明はスルホン化ポリサルホン膜形成材料
の製造法に係り、スルホン化ポリサルホン膜形成材料の
製造は、スルホン化ポリサルホンの非プロトン性極性溶
媒−水混合溶媒溶液と一般式 で表わされる界面活性剤化合物の水溶液を混合し、スル
ホン化ポリサルホンを沈殿させることにより行われる。Therefore, the present invention relates to a method for producing a sulfonated polysulfone film-forming material, and the production of the sulfonated polysulfone film-forming material is performed by using an aprotic polar solvent-water mixed solvent solution of sulfonated polysulfone and a general formula. It is carried out by mixing an aqueous solution of a surfactant compound represented by and precipitating the sulfonated polysulfone.
スルホン化ポリサルホンとしては、スルホン化度が約
0.3〜3.0、好ましくは約0.7〜1.5のものが用いられ、こ
れは一旦非プロトン性極性溶媒−水混合溶媒溶液（濃度
約10〜20重量％）に調製される。As a sulfonated polysulfone, the degree of sulfonation is about
0.3 to 3.0, preferably about 0.7 to 1.5 is used, which is once prepared as an aprotic polar solvent-water mixed solvent solution (concentration of about 10 to 20% by weight).
非プロトン性極性溶媒としては、ジメチルホルムアミ
ド、ジエチルホルムアミド、ジメチルアセトアミド、ジ
エチルアセトアミド、ジメチルスルホキシド、Ｎ−メチ
ル−２−ピロリドン、トリエチルホスフェートなどが用
いられ、これが一般に濃度約10〜30重量％で水との混合
溶媒として用いられる。As the aprotic polar solvent, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, triethylphosphate and the like are used, which are generally used at a concentration of about 10 to 30% by weight with water. Used as a mixed solvent of.
界面活性剤化合物としては、一般式 で表わされるもの、好ましくはブロマイドが、一般に約
１〜５重量％の水溶液として用いられる。このようなジ
高級アルキル基を有する第４アンモニウムハライドの代
りに、やはり正荷電を有するモノ高級アルキル基を有す
る第４アンモニウムハライドを用いると沈殿を生じな
い。The surfactant compound has a general formula , Preferably bromide, is generally used as an aqueous solution of about 1-5% by weight. If a quaternary ammonium halide having a mono-higher alkyl group also having a positive charge is used instead of the quaternary ammonium halide having a di-higher alkyl group, precipitation does not occur.
これら２種類の水溶液を混合すると、そこにスルホン
化ポリサルホンの沈殿が生じるが、これはスルホン化ポ
リサルホンのスルホン基に対し約0.7〜1.1の当量比で用
いられる界面活性剤化合物がイオン結合し、水に不溶性
の物質を形成して沈殿するものと考えられる。沈殿した
スルホン化ポリサルホンは、ロ別、水洗、乾燥して製膜
材料として用いられる。When these two kinds of aqueous solutions are mixed, precipitation of sulfonated polysulfone occurs therein. This is because the surfactant compound used in an equivalent ratio of about 0.7 to 1.1 to the sulfone group of the sulfonated polysulfone is ion-bonded to form water. It is considered that the substance forms an insoluble substance and precipitates. The precipitated sulfonated polysulfone is filtered, washed with water and dried to be used as a film-forming material.
本発明方法により得られる膜形成材料としてのスルホ
ン化ポリサルホンは、乾湿式法により平膜状、中空糸状
などに製膜することができ、得られた膜状物は限外ロ過
膜などとして用いられた場合、長時間水中に放置しても
安定で、膜強度などの低下がみられない。The sulfonated polysulfone as a film-forming material obtained by the method of the present invention can be formed into a flat film shape, a hollow fiber shape, etc. by a dry-wet method, and the obtained film-like material is used as an ultrafiltration membrane or the like. When it is exposed, it is stable even if it is left in water for a long time, and no decrease in film strength is observed.
また、前記したスルホン化ポリサルホンのポリサルホ
ンとの混合物は、必ずしも均一な水溶液を形成しない場
合があり、それを用いての製膜過程では両者の相分離が
生じ、膜として用いた場合にスルホン化ポリサルホンか
ら形成された部分の水に対する安定性の点で不安がみら
れるが、本発明方法によって得られたスルホン化ポリサ
ルホンを用いた場合には、もはやそのようなことはな
い。In addition, a mixture of the above-mentioned sulfonated polysulfone and polysulfone may not always form a uniform aqueous solution, and phase separation occurs between the two in the film-forming process using the sulfonated polysulfone. There is concern about the water stability of the part formed from the, but this is no longer the case when using the sulfonated polysulfones obtained by the process according to the invention.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１ スルホン化ポリサルホン（スルホン化度1.1）1gを、
ジメチルホルムアミド−水（重量比20:80）混合溶媒溶
液10mlに溶解させた。この水溶液と、ジオクタデシルジ
メチルアンモニウムブロマイドの1.5重量％水溶液100ml
を混合すると、スルホン化ポリサルホンが沈殿した。Example 1 1 g of sulfonated polysulfone (sulfonation degree: 1.1)
It was dissolved in 10 ml of a mixed solvent solution of dimethylformamide-water (weight ratio 20:80). This aqueous solution and 100 ml of a 1.5 wt% aqueous solution of dioctadecyldimethylammonium bromide
Upon mixing, the sulfonated polysulfone was precipitated.
実施例２ スルホン化ポリサルホン（スルホン化度0.7）1gを、
ジメチルホルムアミド−水（重量比30:70）混合溶媒溶
液10mlに溶解させた。この水溶液と、ジオクタデシルジ
メチルアンモニウムブロマイドの1.5重量％水溶液100ml
を混合すると、スルホン化ポリサルホンが沈殿した。Example 2 1 g of sulfonated polysulfone (sulfonation degree 0.7)
It was dissolved in 10 ml of a mixed solvent solution of dimethylformamide-water (weight ratio 30:70). This aqueous solution and 100 ml of a 1.5 wt% aqueous solution of dioctadecyldimethylammonium bromide
Upon mixing, the sulfonated polysulfone was precipitated.
実施例３ スルホン化ポリサルホン（スルホン化度1.5）1gを、
ジメチルホルムアミド−水（重量比20:80）混合溶媒溶
液10mlに溶解させた。この水溶液と、ジオクタデシルジ
メチルアンモニウムブロマイドの1.5重量％水溶液100ml
を混合すると、スルホン化ポリサルホンが沈殿した。Example 3 1 g of sulfonated polysulfone (sulfonation degree: 1.5)
It was dissolved in 10 ml of a mixed solvent solution of dimethylformamide-water (weight ratio 20:80). This aqueous solution and 100 ml of a 1.5 wt% aqueous solution of dioctadecyldimethylammonium bromide
Upon mixing, the sulfonated polysulfone was precipitated.
実施例４〜６ 実施例１において、ジオクタデシルジメチルアンモニ
ウムブロマイド水溶液の代りに、ジヘキサデシルジメチ
ルアンモニウムブロマイド、ジテトラデシルジメチルア
ンモニウムブロマイドまたはジドデシルメチルアンモニ
ウムブロマイドの1.5重量％の水溶液100mlを用い、混合
すると、いずれもスルホン化ポリサルホンが沈殿した。Examples 4 to 6 In Example 1, 100 ml of a 1.5 wt% aqueous solution of dihexadecyldimethylammonium bromide, ditetradecyldimethylammonium bromide or didodecylmethylammonium bromide was used in place of the dioctadecyldimethylammonium bromide aqueous solution, and mixed. Then, in each case, the sulfonated polysulfone was precipitated.
以上の各実施例で得られたスルホン化ポリサルホン沈
澱物をロ別、水洗、乾燥し、それぞれ濃度20重量％のジ
メチルホルムアミド溶液を調製し、これらの溶液約5ml
をガラス板上に流延した後、５℃の水中に投入するとゲ
ル化が行われ、得られた平膜状物はいずれも長時間水中
に放置しても溶解したりすることなく安定であった。The sulfonated polysulfone precipitate obtained in each of the above examples was separated by filtration, washed with water and dried to prepare a dimethylformamide solution having a concentration of 20% by weight, and about 5 ml of these solutions were prepared.
After casting on a glass plate, it was poured into water at 5 ° C to cause gelation, and none of the obtained flat film-like products were stable even if left in water for a long time. It was
比較例 実施例６において、ジオクタデシルジメチルアンモニ
ウムブロマイド水溶液の代りに、ドデシルトリメチルア
ンモニウムブロマイドの1.5重量％水溶液を用い、混合
したが、一昼夜放置後にも沈殿は生じなかった。Comparative Example In Example 6, a 1.5 wt% aqueous solution of dodecyltrimethylammonium bromide was used in place of the dioctadecyldimethylammonium bromide aqueous solution, and the mixture was mixed, but no precipitation occurred even after standing overnight.
Claims (5)
性溶媒−水混合溶媒溶液と、一般式 で表わされる界面活性剤化合物の水溶液を混合し、スル
ホン化ポリサルホンを沈殿させることを特徴とするスル
ホン化ポリサルホン膜形成材料の製造法。1. An aprotic polar solvent-water mixed solvent solution of sulfonated polysulfone and a compound of the general formula A method for producing a sulfonated polysulfone film-forming material, which comprises mixing an aqueous solution of a surfactant compound represented by (4) to precipitate the sulfonated polysulfone.
ミドである特許請求の範囲第１項記載の膜形成材料の製
造法。2. The method for producing a film-forming material according to claim 1, wherein the aprotic polar solvent is dimethylformamide.
％の水との混合溶媒溶液が用いられる特許請求の範囲第
１項または第２項記載の膜形成材料の製造法。3. The method for producing a film-forming material according to claim 1 or 2, wherein a mixed solvent solution with water having an aprotic polar solvent concentration of about 10 to 30% by weight is used.
サルホンが用いられる特許請求の範囲第１項記載の膜形
成材料の製造法。4. The method for producing a film-forming material according to claim 1, wherein a sulfonated polysulfone having a sulfonation degree of about 0.3 to 3.0 is used.
囲第１項記載の膜形成材料の製造法。5. The method for producing a film-forming material according to claim 1, which is used for forming an ultrafiltration film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61283935A JPH08175B2 (en) | 1986-11-28 | 1986-11-28 | Method for producing sulfonated polysulfone film forming material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61283935A JPH08175B2 (en) | 1986-11-28 | 1986-11-28 | Method for producing sulfonated polysulfone film forming material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63137703A JPS63137703A (en) | 1988-06-09 |
| JPH08175B2 true JPH08175B2 (en) | 1996-01-10 |
Family
ID=17672121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61283935A Expired - Lifetime JPH08175B2 (en) | 1986-11-28 | 1986-11-28 | Method for producing sulfonated polysulfone film forming material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08175B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348569A (en) * | 1993-06-30 | 1994-09-20 | Praxair Technology, Inc. | Modified poly(phenylene oxide) based membranes for enhanced fluid separation |
| US5356459A (en) * | 1993-06-30 | 1994-10-18 | Praxair Technology, Inc. | Production and use of improved composite fluid separation membranes |
| US5364454A (en) * | 1993-06-30 | 1994-11-15 | Praxair Technology, Inc. | Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form |
-
1986
- 1986-11-28 JP JP61283935A patent/JPH08175B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63137703A (en) | 1988-06-09 |
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